Modification of cellulosic textiles with essentially urea-free compositions comprising n, n&#39;-bis-(methoxymethyl)uron



United States Patent Ofifice 3,369,857 Patented Feb. 20, 1968 3,369,857 MODIFICATION OF CELLULOSIC TEXTILES WITH ESSENTIALLY UREA-FREE COMPO- SITIONS COMPRISING N,N-BIS-(METHOXY- METHYDURON Linton A. Finch and Philip B. Roth, Somerville, NJ., as-

signors to American Cyanamid Company, Stamford, Conn., a corporation of Maine No Drawing. Original application May 21, 1962, Ser. No. 196,499. Divided and this application July 26, 1966, Ser. No. 567,812

3 Claims. (Cl. 8-1162) This application is a divisional application of Ser. No. 196,499 filed May 21, 1962, now abandoned.

This invention relates to novel compositions and in particular to novel water-soluble compositions ideally suited for use as cross-linking or crease proofing agents for cellulosic textile materials, to the process for applying the same to said textiles and to the textile materials finished therewith. Particularly, it relates to such compositions which when applied to cellulosic textile materials will impart improved wrinkle resistance and dimensional stability thereto with an unexpectedly minimal strength loss due to chlorine retention, resulting from the laundering of such materials in the presence of chlorine bleaches.

Aminoplast of the type employed in the impartation of crease resistance to cellulosic textile materials do to varying degrees impart finishes which adversely affect the tensile strength of such materials both initially and as a result of chlorine retention from chlorine bleaching solutions normally employed in the laundering of such materials. This adverse effect normally results when the material so laundered is ironed or calendered during which time hydrochloric acid is formed which causes degradation of the tensile strength of the treated material. Such aminoplasts typically are those resulting from the condensation of urea and its various analogues such as thiourea, the triazines such as the melamines, guanamines and the like with formaldehyde and includes of course their etherified or alkylated derivatives.

Formaldehyde has long been known as a cross-linking agent for cellulosic materials and has been known to impart crease resistance and dimensional stability to such materials. As a reactant, it is known that formaldehyde is difiicult to control to achieve uniform results and in addition is difficult to work with due to its ability to sensitize workmen and its potent disagreeable odor. Moreover, formaldehyde can seriously adversely affect the initial tensile strength values for cellulosic materials finished therewith.

It is the principal object of the present invention to provide novel combinations of aminoplasts and formaldehyde whereby the resulting finish produces unexpectedly minimum losses in tensile strength due to chlorine retention, minimum discoloration due to chlorine retention, unexpectedly low initial tensile strength losses and a uniform and predictable end result.

It is a particular object of the present invention to provide novel combinations of certain specific aminoplasts and formaldehyde whereby the above described improved results are obtained.

Another object is to provide a process for applying crease resisting finishes to cellulosic textile materials employing the above referred to combinations and to provide crease resistant cellulosic textile materials characterized by said improved properties.

In accordance with the present invention novel compositions are provided comprising in relative weight ratios per 100 parts by weight of active components from about 40 to about 95 parts by weight of a highly methylolated aminoplast and from about to about 5 parts by weight of formaldehyde. Preferably, such composi' tions will contain from between about 55 to about 90 parts of a highly methylolated aminoplast and from about 10 to about 45 parts of formaldehyde.

When such compositions are applied to cellulosic textile materials and subsequently dried and cured in ac cordance with the instant invention, the material so finished is characterized by minimum losses in tensile strength due to chlorine retention, low initial tensile strength losses, minimum discoloration due to chlorine retention, and the results are predictable and uniformly obtained.

By the expression highly methylolated aminoplast as that and closely related terms are employed herein it is meant condensation products of polyfunctional compounds characterized by the presence of amino (-NH and imino (=NH) radicals in their molecules and formaldehyde. The present definition is particularly directed to such poly-functional compounds containing at least two amino or imino radicals in their molecules of which at least of the labile hydrogens available for condensation with formaldehyde have been so condensed. Preferably, at least of the available labile hydrogens are condensed with formaldehyde. The alkylated, as for example the methylated, derivatives of such formaldehyde condensates are intended to be contemplated by the above defined term.

It has been our experience that a conventional aminoplast, typical examples of which will be set forth more fully hereinafter, when applied and cured to cellulosic textile materials under normal conditions may become partially demethylolated (due to the loss of combined formaldehyde). Depending on the structure of the aminoplast molecule, demethylolation occurs more rapidly in some, under substantially identical conditions of application and cure, than in others. We have particularly been conscious of the fact that aminoplasts characterized by a high degree of methylolation relative to the theoretical maximum degree of methylolation tend to demethylolate somewhat more rapidly than those which are characterized by a lesser degree of methylolation. It is therefore our theory, but one we do not wish to be bound by, that the inclusion in the composition of large amounts of free formaldehyde produce a sort of mass action which tends to maintain a high degree of methylolation until a substantial portion of the aminoplast has reacted with the cellulosic substrate. We also theorize that the presence of a high percentage of effectively crosslinked aminoplast minimizes unexpectedly the adverse and unpredictable effects which are normally achieved by the curing of formaldehyde on cellulosic textile substrates employing conventional curing procedures.

By the expression cellulose-containing textile mateinit is meant fibers, yarns, filaments, formed fabrics whether knitted, woven or non-woven, felted or otherwise formed containing at least 50% of cellulosic fiber as for example cotton, viscose rayon, linen, flax, jute, ramie or other material which are characteristically cellulosic. These cellulosic textile materials may be employed in combination with other known textile materials as for example they may be blended with other natural or synthetic fibers as for example silk, wool, the acrylic and polyester fibers, the nylons and the like.

By the term formaldehyde as it is employed herein it is meant formaldehyde such as is normally available in 37% or 44% aqueous solutions or the polymeric forms thereof such as para-formaldehyde.

Typical aminoplasts which may be employed in accordance with the present invention are melamineformaldehyde condensates such as those containing from about 4 to 6 moles of combined formaldehyde and optionally from 4 to 6 moles of alcohol, such as for example methyl and ethyl alcohol, although other aliphatic monohydric alcohols and poly alcohols and ether alcohols are also contemplated. Such melamine-formaldehyde condensates may be prepared in general in accordance with the disclosure in the US. Patent 2,197,357 and US. Patent 2,529,856. Typical melamine-formaldehyde condensates employable in accordance with this invention include hexakis(methoxymethyl)melarnine and other substantially fully methylolated melamines and substantially fully etherified substantially fully methylolated melamines. By such terms as they are employed herein it is meant products which contain a minimum of about 5.5 moles of combined formaldehyde per mole of melamine and preferably up to 6 combined moles of formaldehyde and where alkylated it is meant that at least about moles of the available methylol groups on the melamine have been reacted with a suitable alcohol such as methanol, ethanol, various glycols and other alkylating agents as readily suggest themselves to one skilled in the art.

The formaldehyde condensates, urea, thiourea and various of their analogues are contemplated, for example dimethylol urea, alkylated urea-formaldehyde condensates such as methylated dimethylol urea and thiourea, dimethylol ethylene urea, dimethylol ethylene thiourea, dimethylol 1,2-propylene urea and thiourea, dimethylol 1,3-propylene urea and thiourea and other related homologous compounds. In addition, the highly methylolated thiobisamides described in U.S. Patent 2,887,408 are contemplated.

Guanamine-formaldehyde condensates characterized by at least about three of the four availabe labile h drogens condensed with formaldehyde are contemplated as for example those described in U.S. Patent 2,887,409 such as the tetramethylol derivatives of methoxyacetoguanamine, ethoxyacetoguanamine, tertiary butoxyacetoguanamine and the like.

Other typical examples of suitable aminoplasts are the highly methylolated triazones such as are described in U.S. Patent 2,304,624. Thus for example the fully methylolated tetrahydro S-(fi-hydroxyethyl)-5-triazone and other related homologous compounds are contemplated.

A particular and preferred aminoplast contemplated for use in accordance with the present invention are the urons as for example N,N-bis(methoxymethyl)uron which compound and others closely related thereto are described in U.S. Patent 2,373,135.

By the term uron as it is employed herein it is meant the product obtained by the process described by Kadowaki [Bull. Chem. Soc. Japan 11, 248 (1936)] or by modifications of such process Where y urea (1.0 mole) and formaldehyde (4.25 moles) are reacted under neutral conditions and the reaction product then alkylated under strong acid conditions followed by extraction of the product with chloroform or chloroform and ether.

According to the Kadowaki procedures the product was then distilled and N,N-bis(methoxymethyl)uron was obtained. Normally such reaction products will contain substantial amounts of highly methylolated ureas and alkylated methylolated ureas. However, any reaction products containing at least 20% of N,N'-bis(methoxymethyl)uron will -be considered as being a uron reactant. A refined uron will be considered as one having at least 60% of N,N'-bis(methoxymethyl)uron. As will be seen in the examples hereinafter these compounds in the combination of the instant invention demonstrate surprisingly and unexpectedly improved results.

These amioplasts and their equivalents may be employed singly or in combination with one another in accordance with the present invention.

The compositions of this invention are preferably applied from the same bath with a curing accelerator therein. The compositions may be applied to the textile material by any of the conventional techniques in textile finishing as for example spraying, dipping, immersing, padding and the like in such amounts as to apply from about 1 to about 25% and in some instances higher amounts of the composition of this invention based on the dry weight of the fabric. Within certain limits the amount of the composition applied depends upon the particular type of fabric being treated. Thus, in treating fabric consisting of cotton fiber the concentration of from 1 to about 25% and preferably from about 2% to 12% based on the dry weight of the fabric are utilized.

Normally the composition of reactants is applied with V a curing catalyst or accelerator. A catalyst utilized may be free acids, acid salts, alkanolamine salts, metal salts and the like. The concentration of catalyst employed may range from about 0.1 to about 35% or higher based on the weight of active components depending upon the particular catalyst or accelerator employed. Thus, for example from about 0.1 to about 10% of free acid such as phosphoric, lactic, tartaric, oxalic and the like may be employed while in the case of ammonium chloride amounts of from between 0.5 and about 10% may be used. In the case of amine salts such as alkanolamine salts such as diethanolamine hydrochloride from about 1.0 to about 10% are most useful, while with respect to salts such as magnesium chloride, zinc chloride, zinc nitrate, aluminum chloride and the like amounts of from between 5 and 35% have been successfully employed. In all instances the concentration of the catalyst is based on the weight of the active com ponents employed.

Following the application of the reactants and the curing accelerator to the cellulosic textile material, the material is normally subject to drying and curing operations to effect the desirable wash and wear properties of crease resistance and shrinkage control. The drying and curing operation may be carried out in a single step or in separate steps. The temperature at which the drying and curing operations are effected vary widely and are influenced to some extent by the type of catalyst employed. Normally the range of temperature extends from about F. to about 450 F. or even higher. Generally speaking, the time of the drying and/ or curing operation is inversely proportional to the temperature employed and of course is influenced by whether or not separate or combined drying and curing steps are employed.

Generally, when drying and curing is carried out in a combined operation a time of from about one minute to about ten minutes may be employed at temperatures at from about 450 to 250 F., respectively. When the fabric: has been dried preliminary to curing, curing times on the: order of five minutes to about one quarter minute at a temperature of from between 250 and 450 F., respec-- tively havebeen successfully employed.

border to illustrate the present invention the following examples are given primarily by way of illustration. No specific details or enumerations contained therein should be construed as limitations on the present invention except as they appear in the appended claims. All parts and percentages are by weight unless otherwise clearly designated.

6 The so-finished cloth was tested after 5 washes at 212 F. and after scorching following chlorine bleaching. The results of these applications are reported in Table I below.

TABLE I Percent Solids Applied (owl) Warp Tensile Strength (lbs.) Percent Ratio Wrinkle Agent: HCHO Percent Recovery Agent 1 Percent Real on Fabric Initial Chlorine Loss After W+F (in 1101- Scorch Scorch Chlorine degrees) Scorch Initial 2. 0 None 1: 0 43 35 19 202 2. 0 0. 6 1: 0. 3 37 34 8 212 2.0 1. 5 1; 0. 75 32 6 233 2.0 2. 4 1: 1. 2 28 30 0 245 Untreated 50 48 4 159 1 Hexamethoxymethylmelamine plus dimethylolethylene urea.

In the following examples the test methods used are identified as follows.

Wrinkle rec0very.--Tentative Test Method 66-195 described in page 165-1960, Technical Manual and Year Book, American Association of Textile Chemists and Colorists-Vol. 36.

Chlorine retenti0n.Tentative Test Method 92-1958 described on page 123 of the above reference.

Tensile strength.--A.S.T.M. Standard-Scott Tensile Test.

Washing test.Washes at 212 F.-Tentative Test Method 96-l960described in page 126-IV E in Table I, Technical Manual and Year Book of American Association of Textile Chemists and Colorists-Vol. 36.

Yellowness index.-Calculated from equation Yellowness Index =70 1 Example 2 The same procedure as was employed in Example 1 was employed with the exception that the agent for reactant is N,N'-bis(methoxymethyl)uron in combination with various other methylolated and alkylated methylolated ureas and hexamethoxymethylolmelamine. This particular uron composition may be described as a crude uron in accordance with the specification set forth above in combination with hexamethoxymethylol melamine.

The results of this application are shown in Table II R577 below.

TABLE II Percent Solids Applied (owl) Warp Tensile Strength (lbs.) Percent Ratio Wrinkle AgentzHCHO Percent Recovery Agent 1 Percent Real on Fabric Initial Chlorine Loss After W+F (in HCHO Scorch Scorch Chlorine degrees) Scorch 2.0 None 1:0 44 33 25 200 2. 0 O. 6 1:0. 3 38 37 3 221 2.0 1. 5 1:0. 75 36 2 220 2. 0 2. 4 1:1. 2 34 30 234 Untreated 48 4 159 1 Crude N ,N'-bis (methoxymethyDuron plus hexamethoxymethylmelamine.

where R and R are reflectance values obtained on a recording spectrophotometer, using a magnesium carbonate block as a reference standard at the wavelengths of 455 millimicrons and 577 millimicrons respectively.

Example 1 Two percent solids of a product containing hexamethoxymethyl melamine in combination with dimethylol ethylene urea was applied to 80 x 80 cotton percale by padding, employing 12% magnesium chloride based on the weight of the hexamethoxymethylmelamine-dimethylol ethyleneurea mixture, plus 2, 5 or 8% of 37% formaldehyde added to the treating bath. (This is 0.74, 1.85 or 2.96% real formaldehyde in the bath.)

The applications were made by immersing the pieces of cloth in their respective treating baths and padding the cloth on a pressure controlled three roll padder, to deposit 0.6, 1.5 or 2.4% real formaldehyde on the fabric. After padding, the swatches were dried for 1.5 minutes at 225 F. and cured for 1.5 minutes at 350 F.

after chlorine scorching and an increase of the wrinkle recover.

Example 3 Five percent total solids of a mixture of N,N'-bis(meth oxymethyl)uron and other urea formaldehyde condensates (a crude uron) alone or formaldehyde alone or combinations of these agents in various ratios were employed using 12% magnesium chloride based on the total active components as the accelerator. Swatches of the material were immersed in the respective baths and then padded, followed by drying at 225 F. for 1.5 minutes and curing at 350 F. for 1.5 minutes.

The warp tensile tests were performed after initial scorching and after chlorine treatment.

The results of these applications appear in Table III hereinbelow.

TABLE III AATCC Chlorine Scorch Test Percent Solids Applied (owf) Ratio Warp Tensile Strength (lbs) Agent:I-IGHO Percent Loss Agent 1 HCHO Initial hloi'ine Alter Chlorine Scorch Scorch Scorch 5 None 100:0 41 64 4. 37 None 100:0 42 12 72 4. 37 0.63 87. 5:12. 5 39 16 59 3. 75 None 100:0 42 12 72 3. 75 1. 75:25 17 58 3. 13 None 100:0 43 12 72 3. 13 1. 87 62. 5:37. 5 42 17 2. 5 None 100:0 48 14 71 2. 5 2. 5 50:50 38 16 58 1. 87 None 100:0 44 16 64 1. 87 3. 13 37. 36 26 28 1. 25 None 1 42 18 57 1. 25 3. 37 29 22 0. 63 None 1 44 25 43 O. 63 4. 37 12. 31 34 6 None 5 100:0 33 32 3 1 Crude N,N-bis(metlioxymethyDuron.

Table III hereinabove shows that the presence of formaldehyde at all of the indicated concentrations decreases the degradation caused by scorching after chlorine' washing. I

Example 4 The procedure here followed is the same as that employed in Example 3 with the exception that an pure N,N-bis(methoxymethyl)uron is substituted for the crude uron.

The results of this application appear in Table IV below.

was prepared by stirring the three components at room emperature. The remaining 50% was water.

An aqueous dilution containing 10.0% active component of the above mixture and 10% anhydrous zinc nitrate (based on the weight of active components) was prepared by diluting the reactant-catalyst combination with water.

Application was made on white broadcloth (144 x 76 count) by immersing the fabric in the prepared dilution, followed by padding through a three-roll padder to obtain approximately 70% wet pick-up equal to 7.0% active material based on the dry weight of the fabric.

TABLE IV AATCC Chlorine Scorch Tensile Tests Percent Solids Applied (owf) Ratio Agcnt:HCHO Warp Tensile Strength, Lbs. Percent Loss Alter Scorch Agent 1 ECHO Initial Scorch C1 Scorch 5 None :0 31 23 26 3. 75 None 100:0 28 18 36 3. 75 1. 25 75:25 30 21 30 3.13 None 100:0 31 25 19 3. 13 1. 87 62. 5:37. 5 32 28 13 '2. 5 None 100 O 31 22 29 2. 5 2. 5 50 :30 30 24 20 1. 25 None 100: 0 31 26 16 1. 25 3. 75 25:75 29 26 10 0. 63 None 100:0 31 25 19 0. 63 4. 37 12. 5 87. 5 29 26 10 Untreated 48 47 2 1 Refined N,N-bis(methoxymethyl)uron.

Table IV above demonstrates that considerably less tensile strength loss after chlorine scorching is obtained by the inclusion of formaldehyde with a refined N,N- bis(methoxymethyl)uron in accordance with the instant invention.

Example 5 A 50% Active Component Composition comprising:

Following the padding, the treated fabric was dried on a pin tenter frame at 225 -F. for 1 minute followed by curing at 250 F. for 1 minute.

A portion of the treated fabric was then tested for initial tensile strength and wrinkle recover. The remaining portion of the treated fabric was subjected to 10 commercial launderings containing a sodium hypochlorite Agents. Parcent by Weight bleach followed by drying after each wash.

N,N-bis(methoxymethyDuron (refined) 17. 15 9 The fabric was then subjected to the standard A.A.T. Hexamethoxymethylmelamine 11.25 -C- C l rin Ret ntion Test as previously noted. Re- Forma-ldehyde 21.6 Sults of these tests are shown in Table V.

The Yellowness Index was determined in the manner Total 50.00 described above.

TABLE V Warp Tensile Strengths (in lbs.) Initial Wrinkle Yellowness Index Treatment of Fabric Recovery After AATCC Chlorine Retention Test After 10 Comm.

W +F (degrees) Initial Initial Alter Washes 10 Comm. Washes Not Scorched Scorched Percent Tensile Loss Treated 29s 42 39 41 36 12 o. 4 Untreated.- 113 81 84 76 0. 4

Table V demonstrates that employing compositions in accordance with this invention results in a finish having excellent wrinkle recovery, minimum tensile strength loss due to score-hing after chlorine bleaching and a yellowing index after laundering which is equal to that of unfinished fabric.

It should be noted that aminoplast crease-proofing agents containing minor amounts of excess formaldehyde or free formaldehyde have long been known. However, such materials are normally characterized by the presence of at most 2 or 3% of free formaldehyde which usually is the result ofthe inability to completely remove ex cess formaldehyde from the condensate after its preparation or is the result of dissociation in stored masses of the condensate. At any rate, such relatively minor amounts of free formaldehyde for the most part do not in any way achieve the surprising results of the substantial amount of free formaldehyde employed in the novel compositions of this invention and are not contemplated thereby.

Other textile finishing resins or agents either thermosetting or thermoplastic may be employed with the compositions of this invention to improve the durability of such finishes or to modify the hand or other characteris-tics of the finished fabric. In addition of course various softeners, stitfeners, lubricants and other conventional textile treating agents and auxiliaries may be employed with the compositions of this invention.

We claim:

L A process for imparting a crease resistant finish to cel-lulosic textile materials characterized by improved resistance to degradation due to chlorine retention which comprises applying a composition consisting essentially of from about 50 to about 90 parts by weight of a N,N'- bis-(methoxymethy1)uron and from about 45 to about 10 parts by weight of formaldehyde and a catalyst therefor, and thereafter curing said composition on the material by the application of heat. I

2. A process according to claim 1 in which the textile material is formed cotton fabric.

3. Finished cellulosic textile material characterized by crease resistance and resistance to loss of tensile strength due to chlorine retention comprising said material having cured thereon a composition of claim 1.

References Cited UNITED STATES PATENTS 3/1960 Poon 8--116.3 X 8/ 196-2 Musser et al. 1l7-139.4 

1. A PROCESS FOR IMPARTING A CREASE RESISTANT FINISH TO CELLULOSIC TEXTILE MATERIALS CHARACTERIZED BY IMPROVED RESISTANCE TO DEGRADATION DUE TO CHLORINE RETENTION WHICH COMPRISES APPLYING A COMPOSITION CONSISTING ESSENTIALLY OF FROM ABOUT 50 TO ABOUT 90 PARTS BY WEIGHT OF A N,N''BIS-(METHOXYMETHYL) URON AND FROM ABOUT 45 TO ABOUT 10 PARTS BY WEIGHT OF FORMALDEHYDE AND A CATALYST THEREFOR, AND THEREAFTER CURING SAID COMPOSITION ON THE MATERIAL BY THE APPLICATION OF HEAT. 